Preparation of (Ti1−xAlx)N films from mixed alkoxide solutions by plasma CVD

(Ti_1−xAl_x)N films were prepared on a Si wafer at 700°C from toluene solution of alkoxides (titanium tetraetoxide and aluminum tri-butoxide) in an Ar/N₂/H₂ plasma by the thermal plasma chemical vapor deposition (CVD) method. The films were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, electrical resistivity, and Vickers micro-hardness. Single phase TiN formed at an Al atomic fraction of 0–0.2, with a mixed TiN and AlN phase occurring up to 0.6 and single phase AlN forming above 0.8. The films had relatively sooth surfaces, 0.4 μm thick at an Al atomic fraction of 0.2, and thickened with increasing Al fraction. The atomic concentration of Ti, Al, N, O, and C determined from their respective XPS areas showed that the Ti and Al contents of the films changes with the solution composition in a complementary way. The impurities were about 10 at.% oxygen and carbon. The electrical resistivity was almost unchanged from the value of 10³ μΩ cm at 0–0.6 Al but then suddenly increased to 10⁴ μΩ cm at higher Al contents. The hardness showed a synergic maximum of about 20 GPa at an Al fraction of 0.6–0.8.     

Characterization of GaN epitaxial layers on SiC substrates with AlxGa1−xN buffer layers

High quality GaN epitaxial layers were obtained with Al_xGa_1−xN buffer layers on 6H–SiC substrates. The low-pressure metalorganic chemical vapor deposition (LP-MOCVD) method was used. The 500 Å thick buffer layers of Al_xGa_1−xN (0≤x≤1) were deposited on SiC substrates at 1025°C. The FWHM of GaN (0004) X-ray curves are 2–3 arcmin, which vary with the Al content in Al_xGa_1−xN buffer layers. An optimum Al content is found to be 0.18. The best GaN epitaxial film has the mobility and carrier concentration about 564 cm² V⁻¹ s⁻¹ and 1.6×10¹⁷ cm⁻³ at 300 K. The splitting diffraction angle between GaN and Al_xGa_1−xN were also analyzed from X-ray diffraction curves.     

Transmission electron microscopy of annealed a-Si1−xCx:H/Al films with different Al grain sizes

The crystallization behavior of a-Si_1−xC_x:H/Al films after annealing has been investigated by transmission electron microscopy and Raman scattering. It is found that the crystallization process is complex and non-uniform, and that both equiaxial and branching Si grains with many twins and stacking faults arise at annealing temperatures as low as 250 °C. Both fine polycrystalline β-SiC grains and fractal-like -SiC aggregates are first observed in a few regions in a-Si_1−xC_x:H/Al films annealed at 350 °C. The increase of the Al grain size can cause a decrease in the crystallization temperature and a rise in the grain growth rate of Si. At higher annealing temperatures, the reaction process SiC+Al→Al₄C₃+Si is predominant.     

Characterization and microstructure of highly preferred oriented lead barium titanate thin films on MgO (100) by sol-gel process

Highly preferred oriented lead barium titanate (Pb_1−x,Ba_x)TiO₃ thin film, with particular emphasis on (Pb_0.5,Ba_0.5)TiO₃, can be obtained by spin-coating on MgO (100) substrate by using the precursor sol, which was synthesized from acetylacetone chelating with titanium isopropoxide and ethylene glycol as a solvent, in the sol-gel process. Film thickness, pyrolysis temperature and heating rate were studied systemically to investigate their influences on the formation of preferred oriented thin films. The highly preferred (001)/(100) oriented thin film could be obtained by the pyrolysis of wet film at 500 °C and annealing at 600 °C at a slow heating rate of 5 °C/min. It is confirmed that the tetragonal perovskite structure of the titanate ceramic decreases with an increase of Ba content in (Pb_1−x,Ba_x)TiO₃. The (001)/(100) oriented films were synthesized from all compositions between x = 0.2 and x = 0.8, at a crystallization temperature of 600 °C. In particular, for the Ba content in the range of x = 0.50.6, highly preferred (001)/(100) planes were observed.     

Preparation and photoelectrochemical properties of Ti1−xVxO2 solid solution thin film photoelectrodes with gradient bandgap

A design of a gradient bandgap Ti_1−xV_xO₂ thin film electrode for wet-type solar cells is provided. The gradient bandgap film electrodes were prepared by heating stacked layers of varying V/Ti ratios using the sol-gel method. A composition gradient was observed for some of the samples by X-ray photoelectron spectroscopy although it was not very large. For the Ti_1−xV_xO₂ film electrodes, conspicuous visible light photoresponse and photoelectrochemical stability were observed. The photocurrent increased with increasing bias potential. However, the photocurrent onset potentials of the Ti_1−xV_xO₂ film electrodes were more positive than those of TiO₂ film electrodes, probably owing to the high surface state density introduced by the diffusion of vanadium ions.     

Sintering behavior and microwave dielectric properties of Bi3(Nb1−xTax)O7 solid solutions

Solid solutions of Bi₃(Nb_1−xTa_x)O₇ (x = 0.0, 0.3, 0.7, 1) were synthesized using solid state reaction method and their microwave dielectric properties were first reported. Pure phase of fluorite-type could be obtained after calcined at 700 °C (2 h)⁻¹ between 0 ≤ x ≤ 1 and Bi₃(Nb_1−xTa_x)O₇ ceramics could be well densified below 990 °C. As x increased from 0.0 to 1.0, saturated density of Bi₃(Nb_1−xTa_x)O₇ ceramics increased from 8.2 to 9.1 g cm⁻³, microwave permittivity decreased from 95 to 65 while Q_f values increasing from 230 to 560 GHz. Substitution of Ta for Nb modified temperature coefficient of resonant frequency τ_f from −113 ppm °C⁻¹ of Bi₃NbO₇ to −70 ppm °C⁻¹ of Bi₃TaO₇. Microwave permittivity, Q_f values and τ_f values were found to correlate strongly with the structure parameters of fluorite solid solutions and the correlation between them was discussed in detail. Considering the low densified temperature and good microwave dielectric proprieties, solid solutions of Bi₃(Nb_1−xTa_x)O₇ ceramics could be a good candidate for low temperature co-fired ceramics application.     

Tungsten–carbon films prepared by reactive sputtering from argon–benzene discharges

Tungsten–carbon thin films have been deposited by reactive (Ar+C₆H₆) DC magnetron sputtering onto various substrates. Deposition onto glass, monocrystalline silicon, tantalum and stainless steel at room temperature yielded W–C films, having XRD patterns corresponding to the structure of heavily disordered W₂C or WC_1−x carbides. The samples deposited upon the Au or Cu foils were nanocrystalline cubic WC_1−x with the grain size of 2.9 nm. Disordered tungsten–carbon films were stable up to 1200°C. Microhardness of the films with disordered W₂C phase was about 5–6 GPa while that of the films with disordered WC_1−x phase was about 17 GPa. The characteristics of films can be understood considering the effects of the incorporation of free carbon and/or carbon–hydrogen fragments into the tungsten carbide layer.     

Optical and electrical properties of p-type AgInSnxS2−x (x = 0–0.04) thin films prepared by spray pyrolysis

AgInSn_xS_2−x (x = 0–0.2) polycrystalline thin films were prepared by the spray pyrolysis technique. The samples were deposited on glass substrates at temperatures of 375 and 400 °C from alcoholic solutions comprising silver acetate, indium chloride, thiourea and tin chloride. All deposited films crystallized in the chalcopyrite structure of AgInS₂. A p-type conductivity was detected in the Sn-doped samples deposited at 375 °C, otherwise they are n-type. The optical properties of AgInSn_xS_2−x (x < 0.2) resemble those of chalcopyrite AgInS₂. Low-temperature PL measurements revealed that Sn occupying an S-site could be the responsible defect for the p-type conductivity observed in AgInSn_xS_2−x (x < 2) thin films.     

Pyroelectric properties of BST/PLT composite thick films with addition of xPbO–(1 − x)B2O3 glass

The Ba_xSr_1−xTiO₃ (BST)/Pb_1−xLa_xTiO₃ (PLT) composite thick films (20 μm) with 12 mol% amount of xPbO–(1 − x)B₂O₃ glass additives (x = 0.2, 0.35, 0.5, 0.65 and 0.8) have been prepared by screen-printing the paste onto the alumina substrates with silver bottom electrode. X-ray diffraction (XRD), scanning electron microscope (SEM) and an impedance analyzer and an electrometer were used to analyze the phase structures, morphologies and dielectric and pyroelectric properties of the composite thick films, respectively. The wetting and infiltration of the liquid phase on the particles results in the densification of the composite thick films sintered at 750 °C. Nice porous structure formed in the composite thick films with xPbO–(1 − x)B₂O₃ glass as the PbO content (x) is 0.5 ≥ x ≥ 0.35, while dense structure formed in these thick films as the PbO content (x) is 0.8 ≥ x ≥ 0.65. The volatilization of the PbO in PLT and the interdiffusion between the PLT and the glass lead to the reduction of the c-axis of the PLT phase. The operating temperature range of our composite thick films is 0–200 °C. At room temperature (20 °C), the BST/PLT composite thick films with 0.35PbO–0.65B₂O₃ glass additives provided low heat capacity and good pyroelectric figure-of-merit because of their porous structure. The pyroelectric coefficient and figure-of-merit F_D are 364 μC/(m² K) and 14.3 μPa^−1/2, respectively. These good pyroelectric properties as well as being able to produce low-cost devices make this kind of thick films a promising candidate for high-performance pyroelectric applications.     

Phase formation process of IrxSi1−x thin films Structure and electrical properties

Experimental data on the phase formation process of amorphous Ir_xSi_1−x thin films with 0.30 ≤ x ≤ 0.41 are presented and discussed in relation to electric transport properties. The structure formation process at temperatures from 300 K up to 1223 K was investigated by means of X-ray diffraction. Distinct phases were observed in the final stage in dependence on the initial composition: Ir₃Si₄, Ir₃Si₅, and IrSi₃. An unknown metastable phase was found in films with a silicon concentration of 61 at.% to 64 at.% after annealing above the crystallization temperature T = 970 K. The crystal structure of this phase was determined by the combined use of X-ray diffraction and electron diffraction. It was found to be monoclinic, basic-face centred with lattice constants a = 1.027 nm, b = 0.796 nm, c = 0.609 nm, and γ = 113.7°. Additionally, microstructure and morphology of the films were investigated by transmission electron microscopy (TEM). The annealing process was studied by means of mechanical stress investigations as well as by electrical resistivity and thermopower measurements. Correlations between the structure, the phase formation and the electrical transport behaviour are discussed on the basis of conduction mechanism.     

Raman spectra of TiN/AlN superlattices

TiN (4.5 nm)/AlN (3, 6, 22 nm) superlattices deposited by DC magnetron sputtering on MgO(001) at a temperature of 850°C exhibit Raman signals. They indicate N and Ti vacancies (as in thick TiN) in TiN_1−x layers (x=3±2%). x is higher for the sample with 3-nm thick AlN layers, which is ascribed to N diffusion from AlN (standing close to the TiN interfaces) to TiN. In comparison to Raman peaks of thick AlN, there are split signals of wurzite AlN phase, and a signal from another phase, which might be defective rocksalt AlN standing close to the TiN interfaces. The Raman signals clearly show interactions between AlN and TiN layers.     

Chemical vapour deposition of molybdenum carbides: aspects of phase stability

Thin films of different molybdenum carbides (δ-MoC_1−x, γ′-MoC_1−x and Mo₂C) have been deposited from a gas mixture of MoCl₅/H₂/C₂H₄ at 800°C by CVD. The H₂ content in the vapour has a strong influence on the phase composition and microstructure. Typically, high H₂ contents lead to the formation of nanocrystalline δ-MoC_1−x films while coarse-grained γ′-MoC_1−x is formed with an H₂-free gas mixture. This phase has previously only been synthesized by carburization of Mo in a CO atmosphere and it has therefore been considered as an oxycarbide phase stabilized by the presence of oxygen in the lattice. Our results, however, show that γ′-MoC_1−x films containing only trace amounts of oxygen can be deposited by CVD. Stability calculations using a FP-LMTO method confirmed that the γ′-MoC_1−x phase is stabilized by oxygen but that the difference in energy between e.g. δ-MoC_0.75 and oxygen-free γ′-MoC_0.75 is small enough to allow the synthesis of the latter phase in the absence of kinetic constraints. Annealing experiments of metastable δ-MoC_1−x and γ′-MoC_1−x films showed two different reaction products suggesting that kinetic effects play an important role in the decomposition of these phases.     

Preparation of SiO2 films with embedded Si nanocrystals by reactive r.f. magnetron sputtering

SiO_x films with a nominal x-value (1≤x≤2) were deposited on flat-surface silicon substrates by reactive r.f. magnetron sputtering at substrate temperatures of 20 and 500°C, respectively. X-ray diffraction and high resolution TEM investigations of SiO_x films with x=1.45 and x=1 show that as-deposited films have an amorphous structure. After annealing, a nucleation of Si nanocrystals was found with increasing size at increasing initial Si concentration and annealing temperature. The weak photoluminescence in the visible region of as-deposited SiO_x films increases remarkably by annealing with dependence on x.     

Synthesis and humidity sensitive properties of nanocrystalline Ba1−xSrxTiO3 thick films

Nanocrystalline Ba_1−xSr_xTiO₃ (x=0, 0.2, 0.4, 0.6, 0.8 and 1.0) precursors were synthesized using the stearic acid gel method. After the precursors had been calcined at 600–950°C for 0.5–1 h, nanocrystalline powders with the cubic perovskite structure were obtained and these were made into thick films. The powder samples were characterized by differential thermal analysis, X-ray diffraction and transmission electron microscopy, and the thick film samples were characterized by scanning electron microscopy and X-ray diffraction. The humidity-sensitive properties of the nanocrystalline Ba_1−xSr_xTiO₃ thick films were investigated. The results show that these nanocrystalline thick films possess higher humidity sensitivity and lower resistance than those of conventional materials.     

Correlations between structural and electrical properties of the oxyfluorides observed in the YOF-BiOF system

An investigation of the YOF-BiOF system at 850°C has allowed to isolate an ordered Y_0.75Bi_0.25OF phase and a Y_1−xBi_xOF solid solution (0.52 ≤ x ≤ 0.95).

For x ≤ 0.80 the structure is of fluorite-type and for 0.80 < x ≤ 0.95 it shows a fluorite derived rhombohedral distortion. Correlations between structural and electrical properties are established and compared with those of the analogous Pb_xMO S_8-y solid solution (0 ≤ x ≤ 0.80).     

Surface segregation and preferential sputtering in thin Al–Ni alloy films

The surface composition of Al_xNi_1−x alloy films was studied by X-ray electron spectroscopy (XPS) after various surface treatments and oxidation at room temperature. Ion etching caused a marked enrichment in Ni of the altered surface layer. After extensive sputtering, bombardment-induced segregation of Al at the outermost surface layer of the films was established. Al segregation to the surface was observed during annealing up to 1200 K. The interaction of oxygen with the surface of the alloy films caused surface segregation of Al, accompanied by preferential oxidation of Al.     

Preparation of B-doped a-Si1−xCx:H films and heterojunction p–i–n solar cells by the Cat-CVD method

B-doped a-Si_1−xC_x:H films for a window layer of Si thin film solar cells have been prepared by the Cat-CVD method. It is found that C is effectively incorporated into the films by using C₂H₂ as a C source gas, where an only little C incorporation is observed from CH₄ and C₂H₆ under similar deposition conditions. Using a-Si_1−xC_x:H films grown from C₂H₂, heterojunction p–i–n solar cells have been prepared by the Cat-CVD method. The cell structure is (SnO₂ Asahi-U)/ZnO/a-Si_1−xC_x:H(p)/a-Si:H(i)/μc-Si:H(n)/Al. The obtained conversion efficiency was 5.4%.     

Physical properties of (La,Sr)Ti(O,N)3 thin films grown by pulsed laser deposition

Thin films of La_xSr_1−xTiO_3+x/2 (x = 0, 0.25, 0.5, 0.75, 1) were grown by laser ablation on two different kinds of substrates (SrTiO₃ (STO) and MgO) and were subsequently ammonolysed to yield the corresponding oxynitrides La_xSr_1−xTi(O,N)₃. For both substrates all films were found to grow epitaxially to the (1 0 0) direction of the cubic perovskite structure, except for x = 0.5 that grew parallel to the (1 1 0) direction. For some of the films TiN was detected as impurity phase. Scanning electron microscopy revealed that the films are dense and homogeneous with thicknesses around 350 nm. Atomic force microscopy showed that the surface roughness of the films varied between 4.2 and 14.1 nm. The employed substrate had a strong influence on the electrical properties. Films grown on STO exhibited a metallic behaviour, in contrast to the films grown on MgO, which were insulating.     

Investigation on the cross sensitivity of NO2 sensors based on In2O3 thin films prepared by sol-gel and vacuum thermal evaporation

In₂O₃ thin films have been prepared from commercially available pure In₂O₃ powders by high vacuum thermal evaporation (HVTE) and from indium iso-propoxide solutions by sol-gel techniques (SG). The films have been deposited on sapphire substrates provided with platinum interdigital sputtered electrodes. The as-deposited HVTE and SG films have been annealed at 500°C for 24 and 1 h, respectively. The film morphology, crystalline phase and chemical composition have been characterised by SEM, glancing angle XRD and XPS techniques. After annealing at 500°C the films’ microstructure turns from amorphous to crystalline with the development of highly crystalline cubic In₂O_3−x (JCPDS card 6-0416). XPS characterisation has revealed the formation of stoichiometric In₂O₃ (HVTE) and nearly stoichiometric In₂O_3−x (SG) after annealing. SEM characterisation has highlighted substantial morphological differences between the SG (highly porous microstructure) and HVTE (denser) films. All the films show the highest sensitivity to NO₂ gas (0.7–7 ppm concentration range), at 250°C working temperature. At this temperature and 0.7 ppm NO₂ the calculated sensitivities (S=R_g/R_a) yield S=10 and S=7 for SG and HVTE, respectively. No cross sensitivity have been found by exposing the In₂O₃ films to CO and CH₄. Negligible H₂O cross has resulted in the 40–80% relative humidity range, as well as to 1 ppm Cl₂ and 10 ppm NO. Only 1000 ppm C₂H₅OH has resulted to have a significant cross to the NO₂ response.     

Spectroscopic ellipsometry analysis of GaAs1 − xNx layers grown by molecular beam epitaxy

In this work, we present the effect of nitrogen incorporation on the dielectric function of GaAsN samples, grown by molecular beam epitaxy (MBE) followed by a rapid thermal annealing (for 90 s at 680 °C). The GaAs_1 − xN_x samples with N content up to 1.5% (x = 0.0%, 0.1%, 0.5%, 1.5%), are investigated using room temperature spectroscopic ellipsometry (SE). The optical transitions in the spectral region around 3 eV are analyzed by fitting analytical critical point line shapes to the second derivative of the dielectric function. It was found that the features associated with E₁ and E₁ + Δ₁ transitions are blue-shifted and become less sharp with increasing nitrogen incorporation, in contrast to the case of E₀ transition energy in GaAs_1 − xN_x. An increase of the split-off Δ₁ energy with nitrogen content was also obtained, in agreement to results found with MOVPE GaAs_1 − xN_x grown samples.